Process for the preparation of monocyclic ketones and their alkyl derivatives having more than nine ring members



Patented Feb. 19, "1929 UNITED STATES 1,702,843 PATENT OFFICE.

v LEOPOLD BUZICKA, OF GENEVA, SWITZERLAND, ASSIGNOR TO M. NAEF (30., 0F

GENEVA, SWITZERLAND,

PROCESS FOR THE PREPA A COMPANY OF SWITZERLAND.

ATION 0F MONOCYCLIC KETONES AND THEIR ALKYL DE- BIVATIVES HAVING MORETHAN NINE RING MEMBERS.

No Drawing. Application filed November 19,

In the prior application Serial No. 36,049 filed June 9, 1925, there isdescribed a process of preparing monocyclic ketones having more thannine ring members, which comprises heating a normal straight chainaliphatic dicarboxylic acid salt of the fourth group of the periodicsystem especially thorium and cerium, said acid having a carbon chaincontaining more than ten carbon atoms, the carboxylic acid groups beinglinked to the end carbons thereof.

It has also been discovered that in a general manner for the preparationof monocyclic ketones having more than nine ring members and of theiralkyl derivatives, from the dicarboxylic acids having more than tencarbon atoms in a normal chain or from their alkyl derivatives, themetals and the compounds of metals belonging to the fourth group of. theperiodic system may advanta-- geously be employed.

According to the present invention titanium, which belongs to the saidmetals, or its compounds such as for instance titanium oxide areemployed either alone or mixed with another metal or metal compoundbelonging to the said fourth group of the periodic system.

It is also advantageous to use a mixtureof several metals of thethirdgroup of the periodic system or of the rare earths, these mixtures beingobtained artificially or otherwise.

Mixtures of the above mentioned dicarboxylic acids or their alkylderivatives, pre-' as perfume as Well as a primary material forpreparing other interesting technical compounds.

Ewample 2.

3-methyltetradecane-LM-dicarbonylic acid and has a smell like that-1926, Serial No. 149,535, and in Switzerland Decemberpared from the pureacids or as they are obtained in certain technical methods or fromnatural products give, according to the present lnvention, mixtures ofthe ketones, or their alkyl derivatives, which, in this form, can alsobe employed in practice.

For obtaining the mentioned monocyclic ketones, it is possible todirectly heat the acids or the acid anhydrides alone or in presence ofmetals or metal compounds at a comparatively high temperature, insteadof first transforming the corresponding dicarboxylic acids into salts.In this case the use of metals of the fourth group of the periodicsystem is also advantageous.

The ketones or their alkyl derivatives obtained by the described processcan be used as perfumes or as primary materials for the preparation ofcompounds.

Example 1.

The titanium salt of 3-methyl-tetradecane- 1.14-dicarboxylic acid isheated, preferably in a vacuum, up to from 300 to 500 degrees centigradeand the distillate obtained therefrom is worked up by fractionaldistillation. The fractions distilling at from to C. at a pressure of0.5 mm. are then treated with semicarbazide or other reagent usuallyemployed for isolating the ketones.

other technically important The formation of the3-methyl-cyclopentadecanone can be represented by the follow ingequation:

A mixture of the titanium and thorium salts of4-methyl-tetradecane-Ll4-discarb0xylic acid is heated and worked up asde- Example 4.

d methyl tetradecane 1.1 1 dicarboxylic acid is heated at about 300 to500 C. and towards the end of the reaction preferablyin a vacuum, withtitanium oxide. The product obtained is worked up as described inExample 3.

Example 5.

The titanium salt of tetradecane-lli-dicarboxylic acid is heated andworked up as described in Example 1. The cycle-pentadecanone is obtainedwhich distills at about 120 C. (at 0.3 mm.) and melts at 63 C.

Example 6.

Tetradecane-l.14rdicarboxylic acid is heat ed at about 300 to 500 6.,towards the end of the reaction preferably in yacuum, with titaniumhydroxide. The distillate resulting therefrom is worked up as describedin Example 5.

Ewample 7.

The anhydride of tetradecane-1.14-dicar-' boxylic acid is heated toabout 300 to 500 G, towards the end of the reaction preferably in avacuum with titanium hydroxide and Worked up as described in Example 5.

Example 8.

A titanium salt of tetradecane-1.14ldicarboxylic' acid is prepared byonly partially v neutralizing this dicarboxylic acid with sodiumhydroxide nium chloride. The resulting titanium salt is decom used byheating and worked up as describe in Example 5.

r (at 0.3 min),

andprecipitating with titalicence Example .9.

fied by crystallization from alcohol and melt-' mg at 184 C. Thislretone boils at 160 C. melts at 72 C. and has a smell which nearlycorresponds to that of civetone. It can therefore be used as a perfumeand as an intermediate for preparing other interesting technicalcompounds; by oxidizing the cyclononadccanone with chromic acidheptadecane-Lli-dicarboxylic acid is formed.

Example 1'0.

A mixture of clohexadecanone is obtained by working up according to themethod described inExample l a mixture of titanium and thorium salts oftetradecane-l.lei-dicarboxylic and pentadecane-1.15-dicarboxylic acid.

1 claim: a

1. A process for the preparation of monocyclic ketoneshaving more thannine ring members comprising heating titanium salts of polymethylenedicarboxylic acids having more than ten carbon atoms in a normal chain,the carboxylic acid groups being linked to the end carbons thereof. 1

2. A process for the preparation of mono cyclic ketones having more thannine ring members comprising heating amixture of titanium and thoriumsalts of polymethylene dicarboxylic acids having more than ten carbonatoms in a normal chain, the carboxylic in this manner be 1cyclopentadecanone and cyacid groups being linked to the end carbonsthereof.

In testimony whereof I aflix LEOPQLD my signature.

RUZICKA.

